Antiseptic compositions containing phenolic bactericides potentiated with phosphonic acid derivatives

ABSTRACT

An antiseptic composition is described containing a phenolic or quaternary ammonium bactericide and, as a potentiating agent, a water-soluble polyphosphonic acid compound having the formula WHEREIN N IS AN INTEGER FROM 2 TO 3 INCLUSIVE, M is a member selected from the group consisting of hydrogen and cations, and Z is a connecting radical equal in valence to n and containing not more than about 12 atoms, exclusive of hydrogen, in chemical combination, as well as compositions containing the foregoing and other additives such as are found in sanitizing compositions, antiseptic detergent compositions, cosmetic compositions, drilling mud compositions and the like.

United States Patent Irani et al.

[54] ANTISEPTIC COMPOSITIONS CONTAINING PHENOLIC BACTERICIDESPOTENTIATED WITH PHOSPHONIC ACID DERIVATIVES I 72] Inventors: Rlyad R.lranl; ll. Evan Roberts, both of [63] Continuation of Ser. No. 352,942,March 18, 1964.

[52] US. Cl ..424/346, 252/8.5, 252/106,

424/204, 424/329 [51 Int. Cl ..A6lk 27/00, A6lk 13/00 [58] Field ofSearch ..424/204, 346

Primary Examiner-Sam Rosen Attorney-Richard W. Stemberg and Roger R.Jones 51 June 20, 1972 [57] ABSTRACT An antiseptic composition isdescribed containing a phenolic or quaternary ammonium bactericide and,as a potentiating' agent, a water-soluble polyphosphonic acid compoundhaving theformula wherein n is an integer from 2 to 3 inclusive, M is amember selected from the group consisting of hydrogen and cations, and Zis a connecting radical equal in valence to n and containing not morethan about 12 atoms, exclusive of hydrogen, in chemical combination, aswell as compositions containing the foregoing and other additives suchas are found in sanitizing compositions, antiseptic detergentcompositions, cosmetic compositions, drilling mud compositions and thelike.

5 Claims, No Drawings .ANTISEPTIC COMPOSITIONS CONTAINING PIIENOLICBACTERICIDES POTENTIATED WITII PHOSPIIONIC ACID DERIVATIVES This case isa continuation of applicants parent application, Ser. No. 352,942 filedMar. 18, 1964.

This invention relates to improved antiseptic compositions and moreparticularly to the use of potentiating agents which are capable ofimproving the performance of phenolic and quaternary ammoniumbactericides and the compositions resulting therefrom.

In many applications where phenolic and quaternary ammonium bactericidesare useful, it is oftentimes desirable to either increase thebactericidal activity of the bactericide without increasing itsconcentration or to decrease the concentration of the bactericidewithout imparing its efficiency. In addition, in many applications wherethe bactericide is formulated with many other additives, such assurfactants, wetting agents and the like, for example, as in sanitizingcompositions, antiseptic detergent and cosmetic compositions, and thelike, the additives, although compatible with the bactericide may maskor impair its activity, thereby requiring greater amounts of thebactericide in order to achieve the desired degree of activity. As canbe appreciated, therefore, a potentiating agent which is capable ofimproving the performance agent which is capable of improving theperformance of the bactericide in applications such as those describedabove would represent an advancement in this art.

It is, therefore, an object of this invention to provide an improvedantiseptic composition.

It is a further object of this invention to provide a potentiating agentwhich improves the activity of the phenolic and quaternary ammoniumbactericides.

It is still a further object of this invention to provide a potentiatingagent which improves the activity of the phenolic and quaternaryammonium bactericides in the presence of additives such as are found insanitizing compositions, antiseptic detergent compositions, cosmeticcompositions, drilling mud compositions and the like.

These and other objects will become apparent from a reading of thefollowing detailed description.

It has been found that phenolic and/or quaternary ammonium bactericidescan be improved in performance or bactericidal activity by the use of apolyphosphonic acid compound as a potentiating agent, said compoundhaving the following formula wherein n is an integer from 2 to 3inclusive, M is a member selected from the group consisting of hydrogenand cations, and Z is a connecting radial equal in valence to n andcontaining not more than about 12 atoms, exclusive of hydrogen, inchemical combination. The chemical nature of the connecting radical isrelatively unimportant and can include such radicals as hydrocarbylradicals, hydrocarbyl substituted amine radicals, hydrocarbyloxyradicals, and the like. Preferably Z is an alkylidene radical, ahalo-substituted alkylidene radical (especially chloro), ahydroxy-substituted alkylidene radical, a dialkylidene amine radical ora trialkylidene amine radical, and especially an alkylidene radical or atrialkylidene amine radical. Especially preferred are the connectingradicals wherein the alkylidene radical contains about 9 carbon atoms orless and more especially preferred for the alkylidene amine radicals arethe symmetrical alkylidene amine radicals. in addition, the term cationmeans, as used herein, the alkali metal ions, ammonium ions and amineions.

f the polyphosphonic acids, the amino tri-(lower alkylidene phosphonicacids) as well as their water-soluble salts and the lower alkylidenediphosphonic acids as well as their water-soluble salts are preferred.

The amino tri(lower alkylidene phosphonic acids) have the followingformula i Ii/ Y OH 3 wherein X and Y are members selected from the groupconsisting of hydrogen and lower alkyl (1-4 carbon atoms).

The lower alkylidene diphosphonic acids have the following formula X 0OM J l i 9" wherein X is a member selected from the group consisting ofhydrogen and lower alkyl (1-4 carbon atoms) and Y is a member selectedfrom the group consisting of hydrogen, hydroxyl and lower alkyl 1-4carbon atoms).

Amino tri(lower alkylidene phosphonic acid) compounds illustrative ofthe invention include:

1. amino tri(methylene phosphonic acid) 2. amino tri(ethylidenephosphonic acid) 3. amino tri(isopropylidene phosphonic acid) 4. aminodi(methylene phosphonic acid) mono(ethylidene ester by the followinggeneral reaction:

a s [(B0) 1 (I ]N Y 3 wherein X and Y are the same as in the foregoinggeneral formula (2) and R represents an alkyl group.

The free amino tri(lower alkylidene phosphonic acids) and their saltsmay be prepared by hydrolysis of the ester using strong mineral acidssuch as hydrochloric acid and the like.

The lower alkylidene diphosphonic acids and their salts may be preparedby various means, one of which comprises as a first step the preparationof the corresponding ester by the following general reactions:

1. For the alkylidene diphosphonic acids and their salts.

2. For the methylene diphosphonic acid and its salts. 2P(0R), CICH,P(O)(OR),CH,[P(O) (011),], RCI

3. For the l-hydroxy alkylidene diphosphonic acids and their salts.XC(O)P(O)(OR), HP()(OR),:.:.' XC(OH) [l=(0)(OR),] wherein X and Y arethe same as in the foregoing general formula (3) and R represents analkyl group.

The free lower alkylidene diphosphonic acids and their salts may beprepared by hydrolysis of the ester using strong mineral acids such ashydrochloric acid and the like.

Although the polyphosphonic acid compounds are suitable for use inantiseptic compositions, the water-soluble salts of the phosphoric acidcompounds are, in general, preferred in practicing the presentinvention. Of the salts of the amino tri(lower alkylidene phosphonicacid) compounds, the pentametal and di-metal salts are preferred,especially the penta-alkali metal and di-alkali metal salts and inparticular, the pentasodium and di-sodium salts, although other alkalimetal salts, such as potassium, lithium and the like, as well asmixtures of the alkali metal salts, may be substituted therefore. 0f thesalts of the lower alkylidene diphosphonic acid compounds, thetetra-alkali metal salts are preferred, especially the tetra sodium,although other alkali metal salts, such as potassium, lithium and thelike, as well as mixtures of the alkali metal salts may be substitutedtherefore. Other water-soluble acid salts which may be employed inpracticing the present invention include the ammonium salts and aminesalts, particularly when the amine is a low molecular weight amine,i.e., having a molecular weight below about 200, and more particularlythe alkyl amines, alkylene amines, and alkanolamines containing not morethan 2 amine groups. In general, the salts may be prepared byneutralizing the polyphosphonic acid compounds with a base that containsessentially the desired cation. For example, to prepare the disodiumsalt, one of the polyphosphonic acid compounds can be neutralized with astoichiometric amount of a base containing the sodium cation, such asNaOl-l, Na CO and the like.

As previously mentioned, the potentiating agents of the presentinvention can be used with any of the conventional phenolic andquaternary ammonium type bactericides.

The phenolic type bactericides include many compounds which areconsidered phenolic derivatives and which are believed to functioneither as a gross protoplasmic poison or by the inactivation ofessential enzyme systems. Such bactericides include phenol and thefollowing phenolic derivatives including the salts thereof andparticularly the sodium salts:

l. Alkyl phenols which include the following:

butylphenol amylphenol heptylphenol octylphenol 2. Bis-phenols includingthe halogen substituted bis-phenols which include the following:2,2'-methylene bis(4-chlorophenol) 2,2-methylene bis(4,6-dichlorophenol)2,2-methylene bis( 3,4,6-trichlorophenol) 2,2-thiobis(4,6-dichlorophenol) 2,2-thio bis(3,4,6-trichlorophenol)2,2-methylene bis(3-trifluoro methyl-4-chlorophenol) 2,2'-methylenebis(4-chloro-3,5-xylenol) 6,6'-methylene bis(4-chloro-a-phenyl-o-cresol)2,2'-ethylidene bis(3,4,6-trichlorophenol) 3, Bis( hydroxyphenyl)alkanes which include the following:

1,3 bis(p-hydroxyphenyl) butane 1,3 bis(p-hydroxyphenyl) octane 4,6bis(p-hydroxy phenyl) nonane bis(p-hydroxyphenol) methylene bis(p-hydroxyphenyl) ethylene bis (p-hydroxyphenyl) hexamethylene 4.l-lalogenated phenolics which include the following:

p-chlorophenol 3-methyl-p-chlorophenol 3,5-dimethyl-p-chlorophenol6-ethyl-3-methyl-p-chlorphenol 6-diethylmethyl-3-methyl-p-chlorophenolo-bcnzyl-p-chlorophenol o-benzyl-m,m-dimethyl-p-chlorophenolo-phenylethyl-p-chlorophenol o-chlorophenol n-propyl-o-chlorophenoln-amyl-o-chlorophenol tert amyl-o-chlorophenol p-bromophenolmethyl-p-bromophenol n-propyl-bromophenol n-hexyl-bromophenolo-bromophenol tert amyl-o-bromo phenol n-hexyl-o-bromo phenolpentachlorophenol 2,4,6-trichloro phenol S. Dihydric phenolicderivatives which include the followmg: resorcinol methyl resorcinoln-amyl resorcinol n-heptyl resorcinol n-nonyl resorcinol phenylresorcinol benzyl resorcinol p-chlorobenzyl resorcinol 4-n-butylresorcinol 6. Trihydric phenolic derivatives which include the followmg:4-n-hexylpyrogallol 4-n-octyl pyrogallol 4-n-heptyl pyrogallol4-n-heptneyl pyrogallol beuzyl pyrogallol phenyl propyl pyrogallol 7.Hydroxy carboxylic acids and esters which include the following: propylp-hydroxy benzoate butyl p-hydroxy benzoate o-hydroxy benzoic acidm-hydroxy benzoic acid 3-nitro-4-hydroxy benzoic acid 8. Nitrophenolswhich include the following:

m-nitrophenol p-nitrophenol o-nitrophenol 2,4-dinitrophenol2,5-dinitrophenol 2,4,6-trinitrophenol 9. Aminophenols which include thefollowing:

p-aminophenol o-aminophenol ethyl-p-amino phenol 2,4-diamino phenol l0.Naphthol derivatives which include the following:

alpha naphthol beta naphthol tribromo naphthol tetrabromo naphtholQuaternary ammonium bactericides which are suitable are preferablycationic surface-active compounds in which one substituent on thequaternary ammonium nitrogen is lipophilic and the lipophilic groupfonns part of the cation when the compound is dissolved in water. Inaddition, these compounds are believed to function as bactericides bytheir efi'ect on the metabolism or respitory system of themicroorganism. Such bactericides include the following:

1. Lipophilic group directly attached to the quaternary ammoniumnitrogen such as those derived from naturally occuring fatty acids whichinclude the following: dimethyl-decyl-benzyl ammonium chloridediethyl-dodecyl-benzyl ammonium bromide dimethyl-dodecyl-benzyl ammoniumbromide allyl-dibutyl-dodecyl ammonium bromide methyl-diallyl-dodecylammonium iodide diethyl-acetonyl-dodecyl ammonium chloridedimethyl-benzyl-dodecyl ammonium chloride dimethyl-tridecyl-benzylammonium chloride diethyl-pentadecyl-benzyl ammonium bromidedipropyl-phenylethyl-dodecyl ammonium bromidedimethyl-decyl-dimethylbenzyl ammonium chloridedimethyl-dodecyl-dimethylbenzyl ammonium chloridedimethyl-octadecyl-dimethylbenzyl ammonium chloridedimethyl-decyl-ethylbenzyl ammonium chloridedimethyl-dodecyl-ethylbenzyl ammonium chloridedimethyl-hexadecyl-ethbenzyl ammonium chloridetrimethyl-decyltolylmethyl ammonium chloridetrimethyl-tetradecyltolylmethyl ammonium chloride trimethyl-tetradecylammonium chloride dimethyl-didecyl ammonium chloridedimethyl-ditetradecyl ammonium chloride dimethyl-didodecyl ammoniumchloride 2. Lipophilic groups attached to quaternary ammonium nitrogenthrough amide linkage which includes the following:N-trimethyl-N-chloro-N-dodecyl-glycinamideN-trimethyl-N-chloro-Nbenzyl-N'-dodecylglycinamideN-methyl-N-benzyl-N-cyclohexyl-N-chloro-dodecylglycinamideN-methyl-N-benzyl-N-cyclohexyl-N-chloro-N'-dodecylglycinamideN-pentyl-N-benzyl-N-chloro-dodecyl-glycinamide 3. Lipophilic groupattached to quaternary ammonium nitrogen through ester linkage whichincludes the followmg: N-diethyl-N-benzyl-N-(para-cetylaminophenoxyethyl)- ammonium chloridediethyl-N-benzyl-N-(3-butyloxyphenoxyethyl)-ammonium chlorideN-diethyl-N-benzyl-N-(3-n-octyloxyphenoxyethyl)-ammonium chlorideN-diethyl-N-benzyl-N-(n-octyloxyphenthioethyl)-ammonium chlorideN-diethyl-N-benzyl-N-(3-octylthiophenoxyethyl)-ammonium chlorideN-diethyl-N-benzyI-N-(3-butyl amino-4-cresyloxy-ethyl)- ammoniumchloridemethyl-cyclohexyl-ethyl-(a-dodecyloxy-fl-hydroxypropyl)-ammonium iodidetrimethyl-n-octyl oxyethyl ammonium bromidemethyl-diethyl-decyloxyethyl-ammonium iodide 4. Lipophilic groupattached to quaternary ammonium nitrogen through ether linkage whichincludes the followmg: benzyldimethyl-{2-[2-(m-methyl-p-1,1,3,S-tetramethylbutyl phenoxy) ethoxy1ethyl} ammonium chloride benzyldimethyl- 2[2(p-l,l,3,3-tetramethyl phenoxy) ethoxy1ethyl} ammoniumchloride 5. Lipophilic group attached to quaternary ammonium nitrogenthrough a sulfur linkage which includes the following:trimethyl-dodecylthiomethyl-ammonium chloridetributyl-dodecylthiomethyl-ammonium chloridedimethyl-hydroxyethyl-dodecylthio-methyl-ammonium chloridetrihydroxyethyl-dodecylthiomethyl-ammonium chloride methyl-diethyl-octylthioethyl-ammonium iodide 6. Lipophilic group attached to quaternaryammonium nitrogen through heterocyclic ring structure which includes thefollowing: 2-(2-methylnonyl)pyridine sulfate 2-( 2-rnethyldecyl)pyridine sulfate 2-( Z-methyl dodecyl)pyridine sulfate Z-tridecylpyridine sulfate Z-heptadecyl pyridine sulfate 2-(2-methylhexadecyl)pyridine sulfate Z-dodecyl isoquinolinium bromide l'hexadecylpyridinium chloride 2-octyl-l-(2-hydroxyethyl)-imidazolinium chloride2-dodecyl-l-( Z-hydroxyethyl)-imidazolinium chloride 2-tetradecyl-l-(2-hydroxyethyl)-imidazolinium chloride butyl 6-hexyloxy benzylquinolinium chloride o-benzyloxy-benzyl-quinolinium chloride6-dodecyloxy-benzyl-quinolinium chloride 7-dodecyloxy-benzyl-quinoliniumchloride benzyl-decyl-piperidinium bromide benzyl-decyl-pyperidiniumchloride N-crotyl-N-octadecylpiperidinium bromide The amounts of thepotentiating agents which are suitable for improving the activity of thephenolic and/or quaternary ammonium bactericides depend upon, interalia, the end use application and desired degree of potentiation. Ingeneral, the amounts preferred on a weight ratio of bactericide topotentiating agent are from about 1:100 to 10:1.

The invention is not to be limited to any particular method of preparingthe antiseptic composition. The potentiating agent and bactericide canbe admixed in any of the forms in which they are manufactured, as wellas being added simultaneously or separately to an aqueous solution. inany event, the potentiating agent is intended to be used with thebactericide at the time of application of the bactericide.

The resulting antiseptic composition, that is, the potentiating agentand the bactericide, of the present invention is generally effectivewhen used in conventional amounts such as are normally used for thephenolic and/or quaternary ammonium compounds and which, of course,varies depending upon, inter alia, the end use application, types ofmicroorganism which are to be inactivated and the like. Although thephenolic and quaternary ammonium compounds are termed herein asbactericides, that is, an agent capable of killing both pathogenic andnon-pathogenic bacteria, such compounds can, in most cases, be used inconcentrations which can inhibit or prevent the growth of such bacteriaand, therefore, the resulting composition is antiseptic, that is, whenapplied to microorganisms will render them innocuous either by killingthem or preventing their growth.

The following examples are presented for illustrative purposes withparts by weight being given unless otherwise indicated.

EXAMPLE 1 Into a conventional 3-necked, 3-liter flask fitted with areflux condenser, stirrer and thennometer are added about 600 parts ofdiethyl phosphite and about 127.5 parts of 29 percent aqueous ammoniasolution. The flask is placed in an ice bath and after the mixturebecomes cooled to about 0 C about 325 parts of 37 percent aqueousformaldehyde solution are added. The flask is removed from the ice bathand heated with the reaction occurring at about 100 C. After thereaction is completed the flask is allowed to cool to room temperatureand the reaction products are extracted with benzene and separated byfractional distillation. Hexaethyl aminotri(methylene phosphonate)distills between l-200 "C at a pressure of .1 mm and is obtained in aquantity of about 184 parts. The following are the results to enable acomparison between the calculated constituents and found constituents:

Calculated Found 36.87% C, 7.30% H, 38.54% C, 7.76% H,

20.01% P l9.89% P EXAMPLE 2 In a reaction vessel about 299 parts ofamino tri(methylene phosphonic acid) are added to about 800 parts ofa 10percent by weight sodium hydroxide solution and the resulting reactionproduct evaporated to dryness at about 130 C. The resulting product isdisodium amino tri(methylene phosphonate).

EXAMPLE 3 Into a reaction vessel are charged about 18.6 parts of diethylchloromethylphosphonate and about 32.2 parts of triethyl phosphite. Thismixture is stirred and heated to reflux. A bubbler attached to theotherwise closed system checks the ethyl chloride evolution. At l60 Cthe ethyl chloride comes off at a steady rate. After 17 hours ofrefluxing, the temperature reaches about 220 C and the gas evolutionbecomes quite slow. The mixture is cooled to room temperature and vacuumdistilled. The tetraethyl methylenediphosphonate, (C H O)- OPCH PO(OC Hboils at mm a yield of 77% based on the diethyl chloromethylphosphonatereactant. The free acid, methylene diphosphonic acid, H2C(P(O)(OH)-1)2,is prepared by hydrolysis of a portion of the foregoing prepared ester.In a flask similar to that described above 80 grams of the ester isrefluxed with about 400 ml of concentrated hydrochloric acid for aperiod of about 24 hours. The free acid, a sirupy liquid, crystallizeson prolonged standing (about 1 week) in a dessicator.

EXAMPLE 4 In a reaction vessel about 178 parts of methylene diphosphonicacid are added to about 800 parts of a 10% by weight sodium hydraulicsolution and the resulting reaction product evaporated to dryness atabout 130 C. The resulting product is disodium methylene diphosphonate.

EXAMPLE 5 Into a reaction vessel are charged about 60 parts of diethylacetyl phosphonate and about 46 parts of diethyl phosphonate and treatedwith a catalytic amount of sodium ethoxide in ethanol. The reaction isexothermic with the temperature rising to about 70 C. The reactionproduct, tetra ethyl l-hydroxy ethylidene diphosphonate, CHC(H)[P(O)(OC,H has a melting point at about 38-39" C. The free acid, 1-hydroxy, ethylidene diphosphonic acid, CH C(Ol-I)[P (O)(OH) is preparedby hydrolysis of a portion of the foregoing prepared ester. In areaction vessel about 20 grams of the ester and about 100 ml ofconcentrated hydrochloric acid is heated at about l00 C for about 2hours. The free acid is dried in a rotary vacuum evaporator to formcrystals.

EXAMPLE 6 In a reaction vessel about 209 parts of l-hydroxy ethylidenediphosphonic acid are added to about 800 parts of a 10 percent by weightof sodium hydroxide solution and the resulting reaction productevaporated to dryness at about 130 C. The resulting product is disodiuml-hydroxy, ethylidene diphosphonate.

The polyphosphonic acid compounds of the present invention are gooddetergent builders, sequestering agents, and deflocculating agents, andhave the added advantages of being stable, dry, free flowing compoundswhich are relatively water soluble and are hydrolytically stable, thatis, resistant to hydrolysis or degradation under various pH andtemperature conditions. Therefore, such compounds can advantageously beutilized as potentiating agents as well as taking advantage of theirforegoing described properties in many and various applications wherebactericides are used.

The potentiating agents of the present invention have the addedadvantage of improving the activity of the phenolic bactericides in thepresence of anionic, nonionic and/or amphoteric surface active agentswhich are suitable as cleansing agents as well as improving the activityof quaternary ammonium bactericides in the presence of nonionic surfaceactive agents which are suitable as cleansing agents.

Anionic surface active compounds can be broadly described as compoundswhich contain hydrophilic and lyophilic groups in their molecularstructure and which ionize in an aqueous medium to give anionscontaining the lyophilic group. These compounds are usually soap i.e.,an alkali metal or amine salt of a fatty acid and/or fatty acid mixture,the alkali metal salts of organic sulfonates or sulfates. particularlythe sodium salts, such as alkyl aryl sulfonates (e.g. sodium dodecylbenzene sulfonate), sulfate of straight chain primary alcohols (e.g.,sodium lauryl sulfate) and the like. Nonionic surface active compoundscan be broadly described as compounds which do not ionize but acquirehydrophilic characteristics from an oxygenated side chain, usuallypolyoxyethylene, while the lyophilic part of the molecule may come fromfatty acids, phenols, alcohols, amides or amines. For example purposesonly, the polyethylene oxide condensates of alkyl phenols (e.g.condensation product formed from 1 mole nonyl phenol and 10 molesethylene oxide), the condensation products of aliphatic alcohols andethylene oxide (e.g. condensation product formed from 1 mole tridecanoland 12 moles ethylene oxide) are suitable nonionic surface activecompounds in practicing the invention. Amphoteric surface activecompounds can be broadly described as compounds which have both anionicand cationic groups in the same molecule. Examples of such compoundsinclude sodium N- methyl taurate and sodium N-coco beta amino propinate.

Further the potentiating agents of the present invention have the addedadvantage of improving the the activity of the phenolic and quaternaryammonium bactericides in the presence of inorganic builder materialswhich are usually found in sanitizing and antiseptic detergentcompositions, and which are usually comprised of inorganic phosphates,carbonates, sulfates, hydroxides, silicates or combinations thereof,and, in particular, the alkali metal salts of the foregoing materials.The alkali metal salts are preferably the potassium and sodium salts,although ammonium salts may be employed, particularly in combinationwith the potassium or sodium salts. The phosphate compounds arepreferably the chain polyphosphates. Such polyphosphates contain morethan 1 phosphorus atom per molecule, as distinguished fromorthophosphates which contain only one phosphorus atom per molecule.Chain polyphosphates are non-cyclic (and usually linear) phosphates, asdistinguished from ring or cyclic phosphates such as trimetaphosphatesand tetrametaphosphates. Examples of the more common chainpolyphosphates are tetrapotassium pyrophosphate, tetrasodiumpyrophosphate, sodium tripolyphosphate, potassium hexametaphosphate andsodium hexametaphosphate. It should be noted, however, that with mostquaternary ammonium bactericides the pyrophosphates are the only chainpolyphosphates which can advantageously be used.

Other additives which can be utilized are the water-soluble sodium andpotassium silicates. As is well-known, sodium silicates can vary quitewidely in composition, ranging from tetra and disilicates having a moleratio of Na,O:SiO of 1:4 and 1:2, respectively, to the more alkalinesilicates, such as the orthosilicate having a mole ratio of Na,O:SiO of2:1. In general, sodium silicate (Na,O:SiO 1:2) is the preferredsilicate compound for use according to the present invention. However,other silicates, or mixtures of silicates, having an overall mole ratioof Na,O:SiO, between about 1:1 and 1:4 can be used. The carbonates,hydroxides and sulfates are preferably the sodium and potassiumcarbonates, hydroxides and sulfates.

As previously mentioned, the potentiating agents of the presentinvention also exhibit the ability to deflocculate finely divided solidmaterial in an aqueous medium and can advantageously be used, along withbactericides, in drilling mud compositions which contain otheradditives, such as starch and the like, which are subject to degradationor decay by micro-organisms.

The drilling mud compositions contain, as the mud additive, anyconventional type clay material such as hydratable clay or colloidalclay bodies which are capable of being deflocculated or dispersed in anaqueous vehicle and in particular the bentonite type clay consisting ofthe Montmorillonite minerals i.e., Montmorillonite, Beidellite,Nontromite, Hectorite and Saponite. Such clay materials as Wyomingbentonite, commercial medium-yield drilling clays mixed in various partsof the country such as Texas, Tennessee, and Louisiana are among thosewhich are frequently encountered. Weighting material added to increasespecific gravity such as barytes, iron oxide, calcium carbonate, silicaand the like may also be included. The aqueous vehicle may be any typeof suitable fresh or salt water such as is obtained from wells, lakes orthe sea. In addition, the drilling mud compositions of the invention maycontain other additives, such as caustic, starch (corn or modified soyabean), carboxymethylcellulose, co-polymers of ethylene and maleicanhydride, sodium hexametaphosphate, lignosulfonates, quebracho, lime,cement, gypsum and the like.

The compositions containing the bactericide and potentiating agent, aswell as the other additives, such as the surfactants, inorganicmaterials, clays for drilling mud compositions, and the like, aregenerally effective in aqueous systems in conventional amounts anddepending upon the particular composition and the particular applicationthe optimum amounts can readily be determined by simple tests. Usuallyconcentrations of bactericide between about 0.001 percent to aboutpercent are sufficient in most cases, and, as previously mentioned,weight ratios of bactericide to potentiating agent of from about 1:100to 10:1 are preferred although, of course, amounts of the potentiatingagent in excess of 1:100 can be used in the compositions since thepotentiating agents exhibit other highly useful properties such assequestration and deflocculations, and can also be used in thecompositions for these additional properties.

A further understanding of the improved antiseptic compositionsdescribed herein and processes for preparing the compositions will beobtained from the following specific examples which are intended toillustrate this invention, but not to limit the scope thereof, withparts and percentages being by weight unless otherwise indicated.

EXAMPLE 7 A disinfectant composition is prepared formulated as follows:

Additive Parts amino tri(methylene phosphonic acid) 10 phenol 1 rnent,utensils and the like.

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as1,3-bis(phydroxyphenol)butal' fi; P-chlorophenol methyl resorcinol;3-nitro-4-hydroxy-benzoic acid; 2,4-dinitrophenol; and the like, as wellas other potentiating agents such as amino tri(ethylidene phosphonicacid); amino mono(methylene phosphonic acid) di(ethylidene phosphonicacid); methylene rliphosphonic acid; l-hydroxy, ethylidene diphosphonicacid, and the like.

1Q EXAMPLE 8 A disinfectant composition is prepared formulated asfollows:

Additive Parts amino tri( methylene phosphonic acid) 10 mixture ofdodecyl-, tetradecyl-, 1

hexadecyland octadecyl-, dimethyl benzyl ammonium chloride chloride;trimethyl-decyltolyl-methyl ammonium chloride; N-

pentyl-N-benzyl-N-chloro-dodecyl-glycinamide; N-diethyl-N-benzyl-N-(3-butyloxyphenoxyethyl)-ammonium chloride;tributyl-hydroxyethyl-dodecylthio-methylammonium chloride; l-hexadecylpyridinium chloride; and the like, and potentiating agents such as aminotri-(isopropylidene phosphonic acid); amino di(methylene phosphonicacid) mono(ethylidene phosphonic acid); methylene diphosphonic acid;l-hydroxy, ethylidene di-phosphonic acid, and the like.

EXAMPLE 9 A heavy-duty antiseptic detergent composition is preparedformulated as follows:

Additive Parts anionic organic active 30 (sodium cocco fatty alcoholsulfate sodium pentachlorophenate 2 tetrasodium l-hydroxyethylidenediphosphonate 2 sodium tripolyphosphate 38 Na,C0, 15 Na,SO 12 sodiumcarboxymethylcellulose l The above composition is prepared by eitheradmixing the above additives to form a dry, granular admixture oradmixing the above additives in an aqueous medium sufficient to give aslurry of about 50 percent by weight solids and then drying the slurryby conventional means such as drum drying, spray drying and the like.

The above composition, when diluted in water to about 0.2 percentconcentration, exhibits greater bactericidal activity than somecomposition without the tetrasodium l-hydroxy ethylidene diphosphonateand can advantageously be used in commercial laundries and the like forlaundrying bed sheets, diapers and the like.

in addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as sodium2,4,6-trichlorophenate; sodium 3-methyl-pchlorophenate; sodium2,2'-methylene bis(4-chloro-3,5- xylenate); sodium m-hydroxy benzoate,and the like, and potentiating agents such as penta sodium aminotri(methylene phosphonate); penta sodium amino tri(ethylidenephosphonate); tetrasodium methylene diphosphonate; tetrasodiumisopropylidene diphosphonate and the like.

EXAMPLE 10 A heavy-duty antiseptic detergent composition is preparedformulated as follows:

Additive Parts anionic organic active (sodium dodecylbenzene sulfonate)30 2,2'-methylene bis(3,4,6-trichloro phenol) 2 pentasodium aminotri(methylene phosphonate) 30 Na,C; l Na,SO, 22

sodium carboxymethylcellulose l The above composition is prepared byeither admixing the above additives to form a dry, granular admixture oradmixing the above additives in an aqueous medium sufficient to give aslurry of about 50 percent by weight solids and then drying the slurryby conventional means such as drum-drying, spray-drying and the like.

The above composition when diluted in water to about 0.2 percentconcentration exhibits greater bactericidal activity than the samecomposition without the pentasodium amine tri(methylene phosphonate) andcan advantageously be used in commercial laundries and the like forlaundrying bed sheets, diapers and the like.

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as 2,2-thio bis(4,6dichlorophenol); 2,2'-methylene bis(3- trifluoro methyl-4-chlorophenol);butylphenol; obromophenol; 4-n-hexylpyrogallol; ethyl-p-amino phenol andthe like, and potentiating agents such as pentasodium aminotri(ethylidene phosphonate); penta sodium amino tri(isoprylidinephosphonate tetrasodium methylene diphosphonate; tetrasodium l-hydroxy,ethylidene diphosphonate and the like.

EXAMPLE ll A liquid antiseptic detergent composition is preparedformulated as follows:

Additive Parts The above composition is prepared by heating the water toabout 60 C and thereafter adding the above additives to the water in amixer in their above listed order, each additive being added and mixedunder high shear agitation over a period of about 1 to about 7 minuteswhile ensuring that the temperature of the mix does not exceed about80C.

The above composition when diluted in water to about 0.2 percentconcentration exhibits greater bactericidal activity than the samecomposition without pentasodium amino tri(methylene phosphonate) and canadvantageously be used for laundering textiles in relatively cold waterand the like.

In addition, good results can be obtained by using in substantiallysimilar amounts other quaternary ammonium bactericides such asdipropyl-phenylethyl-dodecyl ammonium chloride; dimethyl-hexadecyl-ethylbenzyl ammonium chloride; N-diethyl'N-benzyl-N-(3-butyloxyphenoxyethyl)- ammonium chloride; trimethyl-dodecyl-thiomethyl-ammoniumchloride; l-hexadecylpyridinium chloride, and the like, and potentiatingagents such as pentasodium amino tri-ethylidene phosphonate); pentasodium into amino tri(isoprylidino phosphonate); tetrasodium methylenediphosphonate; tetrasodium l-hydroxy, ethylidene diphosphonate and thelike.

EXAMPLE 12 An antiseptic shampoo composition is prepared formulated asfollows:

The above composition is prepared by melting the potassium stearate atabout 60 C to 70 C and adding thereto the triethanol lauryl sulfate,methyl cellulose, propylene glycol, 2,2'-methylenebis(3,4,6'trichlorophenol) and tetrapotassium l-hydroxyethylidenediphosphonate until the mixture is well mixed and blended and thereafteradding the water in such a manner as to prevent aeration.

The above composition when diluted with water to about 0.2 percentconcentration exhibits greater bactericidal activity than the samecomposition without the tetrapotassium 1- hydroxy ethylidenediphosphonate and, in addition, exhibits good hair cleansing properties.

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as 2,2-methylenebis(4-chlorophenol); 2,2'-methylene bis(4- chloro-3,5-xylenol);p-chlorophenol; 2,4,6-trichlorophenol; oaminophenol; 2,4-dinitrophenoland the like, and potentiating agents such as penta sodium aminotri(methylene phosphonate penta sodium amino tri( ethylidene phosphonatetetrasodium methylene diphosphonate;

tetrasodium isopropylidene diphosphonate, and the like.

EXAMPLE 13 An antiseptic mouthwash composition is prepared formulated asfollows:

Additive Parts ethyl alcohol 10 saccharin 2,2'-methylenebis(3,4,6-trichlorophenol) pentasodium amino tri(methylene phosphonate)sodium lauryl sulfate water The above composition is prepared by addingthe ethyl alcohol, saccharin, 2,2-methylene bis(3,4,6-trichlorophenol),pentasodium amino tri(methylene phosphonate) and sodium lauryl sulfateto the water. This composition when diluted with water at about 1:20 isan effective mouthwash and exhibits greater bactericidal activity thanthe same composition without pentasodium amino tri(methylenephosphonate).

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as 2,2-methylenebis(4-chlorophenol); 2,2'-methylene bis(4- chloro-3 ,5-xylenol);p-chl0rophenol; 2,4,6-trichlorophenol; oaminophenol; 2,4-dinitrophenoland the like, and potentiating agents such as amino tri-(isopropylidenephosphonic acid); amino di(methylene phosphonic acid) mono(ethylidenephosphonic acid); methylene diphosphonic acid; l-hydroxy, ethylidenedi-phosphonic acid, and the like.

EXAMPLE 14 An antiseptic detergent composition is prepared formulated asfollows:

Additive Parts The above composition is prepared by melting the soap ina suitable vessel at about 60 C to 70 C and adding the pentasodium aminotri(methylene phosphonate) and 2,2'-thio bis(4,6-dichlorophenol) to thesoap with agitation. The admixture is then poured into a suitable moldand allowed to solidify by cooling to room temperature (about 25 C).

The above composition when diluted in water to about 0.2 percentconcentration exhibits greater bactericidal activity than the samecomposition without pentasodium amino tri(methylene phosphonate) and isan effective cleanser for hand washing and the like.

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as 2,2'-methylenebis(3,4,6-trichlorophenol); 2,2-methylene bis- (4-chloro-3,5-xylenol);2,2'-ethylidene bis(3,4,6- trichlorophenol);6diethylmethyl-3-methyl-p-chlorophenol and the like, and potentiatingagents such as penta sodium amino tri(ethylidene phosphonate);tetrasodium methylene diphosphonate; tetrasodium isopropylidenediphosphonate, and the like.

EXAMPLE 15 An anteseptic detergent composition is prepared formulated asfollows:

Additive Parts The above composition is prepared by melting the soap ina suitable vessel at about 60 C to 70 C and adding the penta sodiumamino tri(methylene phosphonate) and 2,2- methylenebis(3,4,6-trichlorophenol) to the soap with agitation. The admixture isthen poured into a suitable mold and allowed to solidify by cooling toroom temperature (about 25 C).

The above composition when diluted in water to about 0.2 percentconcentration exhibits greater bactericidal activity then the samecomposition without pentasodium amino tri(methylene phosphonate) and isan effective cleanser for hand washing and the like.

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as 2,2'-methylenebis(4-chlorophcnol); 2,2'-methylene bis(4- chloro-3,5-xylenol);p-chlorophenol; 2,4,6-trichlorophenol; oaminophenol; 2,4-dinitrophenoland the like, and potentiating agents such as amino tri(isopropylidenephosphonic acid); amino di(methylene phosphonic acid) mono(ethylidenephosphonic acid); methylene diphosphonic acid; l-hydroxy, ethylidenedi-phosphonic acid, and the like.

EXAMPLE 16 A detergent-sanitizer composition is prepared formulated asfollows:

Additive Parts nonionic organic active (nonyl phenolethylene oxidecondensate) l0 hexadecyl-dimethyl-benzyl ammonium chloride l0 sodiumcarbonate (light density) 30 tetrasodium pyrophosphate 40 tetrasodiuml-hydroxy, ethylidene diphosphonate ID The above composition is preparedby admixing hexadecyldimethyl-benzyl ammonium chloride, sodiumcarbonate, tetrasodium pyrophosphonate and tetrasodium l-hydroxy,ethylidene diphosphonate to form a granular admixture, and slowly addingthe nonionic organic active under agitation in order to absorb thenonionic on the granular admixture.

The above composition when diluted in water to about 0.2 percentconcentration exhibits greater bactericidal activity than the samecomposition without tetrasodium l-hydroxy, ethylidene phosphonate and isan effective cleanser and sanitizer for milk cans, dairy equipment andthe like.

In addition, good results can be obtained by using in substantiallysimilar amounts other quaternary ammonium bactericides such asdipropyl-phenylethyl-dodecyl ammonium chloride; dimethyl-hexadecyl-ethylbenzyl ammonium chloride; N-diethyl-N-benzyl-N-(3-butyloxyphenoxyethyl)- ammonium chloride; trimethyl-dodecylthiomethyl-ammoniumchloride; l-hexadecyl pyridinium chloride, and the like, andpotentiating agents such as pentasodium amino tri(methylenephosphonate); pentasodium amino tri(ethylidene phosphonate); tetrasodiummethylene diphosphonate; tetrasodium isopropylidene diphosphonate, andthe like.

EXAMPLE 17 An antiseptic bottle washing composition is prepared asfollows:

tetrasodium methylene diphosphonate 6 diethyl-pentadecyl-benzyl ammoniumchloride 2 The above composition when diluted in water to about 2percent concentration exhibits greater bactericidal activity than thesame composition without tetrasodium methylene diphosphonate and is aneffective cleanser for washing milk bottles, beer bottles, and the like.

In addition, good results can be obtained by using in substantiallysimilar amounts other quaternary ammonium bactericides such asdipropyl-phenylethyl-dodecyl ammonium chloride; dimethyl-hexadecyl-ethylbenzyl ammonium chloride; N-diethyl-N-benzyl-N-(S-butyloxyphenoxyethyl)- ammonium chloride; trimethyl-dodecylthiomethyl-ammoniumchloride; l-hexadecyl pyridinium chloride, and the like, andpotentiating agents such as amino tri(methylene phosphonic acid); aminotri-(ethylidene phosphonic acid); 1- hydroxy ethylidene di-phosphonicacid, and the like.

EXAMPIE l8 An antiseptic bottle washing composition is prepared as follows:

sodium silicate (Na,O:Si0, of I22) l dimethyl-dodecyl-benzyl ammoniumchloride 2 In addition, good results can be obtained by using insubstantially similar amounts other quaternary ammonium bactericidessuch as dipropyl-phenylethyl-dodecyl ammonium chloride;dimethyl-hexadecyl-ethyl benzyl ammonium chloride;N-diethyl-N-benzyl-N-(3-butyloxy phenoxyethyl)- ammonium chloride;trimethyldodecylthiomethyl-ammoni- EXAMPLE 19 An antiseptic toothpasteis prepared formulated as follows:

Additive Parts glycerine (95% by weight) 270 carboxymethyl cellulose 9water 180 sodium lauryl sulfate 20 dicalcium phosphate dihydrate 450saccharin 5 pentasodium amino tri(methylene phosphonate) l02,2-methylene bis(3,4,6-trichloro phenol) l The above composition isprepared by heating the glycerine in a suitable mixer and adding thecarboxymethyl cellulose under gentle mixing. The water is then added andthe heating and mixing is continued until the temperature reaches about70 C. After mixing for about 5 minutes the sodium lauryl sulfate isadded and the mixing continued for about 5 more minutes. The heating isdiscontinued and the dicalcium phosphate dihydrate is added in suitableportions and is thoroughly mixed into the paste. The paste is cooled atsuch a rate as will reduce the temperature to about 32 C in about 45minutes and the mixing is continued for an additional minutes at about30 C to 32 C. The flavor is then thoroughly mixed into the paste and thepaste can be put into tubes by conventional methods.

The above composition exhibits greater bactericidal activity than thesame composition without pentasodium amino tri(methylene phosphonate) atconcentrations normally used in brushing teeth.

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as 2,2-rnethylenebis(3,4,6-trichloro-phenol); 2,2-methylene bis- (4-chloro-3,5-xylenol);2,2'-ethylidene bis(3,4,6- trichlorophenol);6-diethylmethyl-3-methyl-p-chlorophenol and the like, and potentiatingagents such as pentasodium amino tri(ethylidene phosphonate) tetrasodiummethylene diphosphonate; tetrasodium isopropylidene diphosphonate, andthe like.

EXAMPLE A disinfecting composition is prepared formulated as follows:

The above composition when in water at about 0.25 percent concentrationkills entirely at about 50 C, a deposit of bacteria coli in about 4minutes while the above composition, without the butylidenediphosphonic, under the same conditions takes more than about 6 minutesto kill a deposit of bacteria coli.

In addition, good results can be obtained by using in substantiallysimilar amounts other quaternary ammonium bactericides such asN-trimethyl-N-chloro-N-dodecyl-glycinamide;N-dimethyl-N-benzyl-N-chloro-dodecyl-glycinamide;N-methyl-N-benzyl-N-cyclohexyl-N-chloro-N-dodecylglycinamide and thelike, and potentiating agents such as pentasodium amino tri( methylenephosphonate); pentasodium amino tri(ethylidene phosphonate); tetrasodiummethylene diphosphonate; tetrasodium sopropylidene diphosphonate, andthe like EXAMPLE 2] To about one part of soya amine is added about 4.5parts of sodium carbonate, about 5 parts of methylene diphosphonic acidand about 5 parts of tri-sodium phosphate. Soya amine is a mixture oftrimethyl alkyl ammonium chloride. The alkyl groups are derived from thefollowing acids: approximately 6.5 percent palmitic, 4.5 percentstearic, 43.5 percent 52.5 percent linoleic and 2.3 percent linoleic.

The admixture when diluted to about 1000 parts with water produces asolution which exhibits greater bactericidal activity than the samecomposition without methylene diphosphonic acid and can advantageouslybe used in cleaning dairy plant equipment such as large vats andpipelines.

In addition, good results can be obtained by using in substantiallysimilar amounts other quaternary ammonium bactericides such asdimethyl-decyl-benzyl ammonium chloride; diethyl-dodecyl-benzyl ammoniumchloride; diethyl-pentadecyl-benzyl ammonium chloride;dimethyl-ditetradecyl ammonium chloride, and the like, and potentiatingagents such as l-hydroxy, propylidene diphosphonic acid; isopropylidenediphosphonic acid; amino di-(methylene phosphonic acid) mono-(ethylidenephosphonic acid) and the like.

EXAMPLE 22 To about 1 part of dodecyl dimethyl benzyl ammonium chlorideis added about 4.5 parts potassium carbonate, and about 5 parts aminotri(methylene phosphonic acid).

The admixture when diluted to about 1000 parts with water produces asolution which exhibits greater bactericidal activity than the samecomposition without amino tri-methylene phosphonic acid) and canadvantageously be used in cleaning dairy plant equipment such as largevats and pipelines.

In addition, good results can be obtained by using in substantiallysimilar amounts other quaternary ammonium bactericides such asdimethyl-decyl-benzyl ammonium chloride; diethyl-dodecyl-benzyl ammoniumchloride; diethyl-pentadecyl-benzyl ammonium chloride;di-methyl-ditetradecyl ammonium chloride, and the like, and potentiatingagents such as l-hydroxy, propylidene di-phosphonic acid; isopropylidenediphosphonic acid; amino di-(methylene phosphonic acid) mono(ethylidenephosphonic acid) and the like.

EXAMPLE 23 To about one part of tallow amine is added about 4.5 parts ofsodium carbonate, about 5 parts of tetrasodium 1- hydroxy, ethylidenediphosphonate and about 5 parts trisodiurn phosphate. Tallow amine is amixture of trimethyl alkyl ammonium chloride. The alkyl group is derivedfrom the following acids: approximately 3 percent myristic, 29 percentpalmitic, 18.5 percent stearate, 46.5 oleic, and 3.0 percent linoleic.

In addition, good results can be obtained by using in substantiallysimilar amounts other quaternary ammonium bactericides such asdimethyl-decyl-benzyl ammonium chloride; diethyl-dodecyl-benzyl ammoniumchloride; diethyl-pentadecyl-benzyl ammonium chloride;di-methyl-ditetradecyl ammonium chloride, and the like, and potentiaingagents such as l-hydroxy, propylidene diphosphonic acid; isopropylidenediphosphonic acid; amino di-(methylene phosphonic acid) mono(ethylidenephosphonic acid) and the like.

This admixture when diluted to about 1000 parts with water produces aclear solution and exhibits greater bactericidal activity than the samecomposition without tetrasodium 1- hydroxy, ethylidene diphosphonate andcan advantageously be used in cleaning dairy plant equipment such aslarge vats and pipelines.

EXAMPLE 24 About 2 parts of hexylphenol, about 5 parts of aminotri(methylene phosphonic acid) and about 93 parts of 91 percent strengthiso-propyl alcohol. About 1 part of this admixture is mixed with 50parts of water and yields a clear transparent solution which is stronglyantiseptic. Its effectiveness against Staphylococcus aureus is four foldover a similar admixture which does not contain the amine tri(methylenephosphonic acid).

The above composition can advantageously be used for the disinfecting ofhospital equipment, instruments, utensils, and the like.

In addition, good results can be obtained by using in sub stantiallysimilar amounts other phenolic bactericides such as butylphenol,arnylphenol, heptyl-phenol, octylphenol and the like, andpotentiating'agents such as amino tri(isopropylidene phosphonic acid);amino di(methylene phosphonic acid) mono(ethylidene phosphonic acid);methylene diphosphonic acid; l-hydroxy, ethylidene diphosphonic acid,and the like.

EXAMPLE 25 An antiseptic drilling mud composition is prepared asfollows:

solids slurry The above additives when blended to form a slurry,exhibit, as a drilling mud composition, good properties for such use.

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as2,4,6-trichlorophenol; n-hexyl-o-bromophenol, tetrachlorophenol and thelike, and potentiating agents such as tetrasodium methylenediphosphonate, tetrasodium 1- hydroxy, ethylidene diphosphonate and thelike.

EXAMPLE 26 An antiseptic lime treated drilling mud composition isprepared as follows:

Addition Parts clay-blend of one part Wyoming bentonite, four partsDixie bond clay and I0 pans Tennessee ball clay calcium hydroxide starchquebracho sodium pentachlorophenol .4 tetrasodium l-hydroxy ethylidenediphosphonate .8

water sufficient to give 35% solids slurry The above additives whenblended to form a slurry, exhibit, as a drilling mud composition, goodproperties for such use.

In addition, good results can be obtained by using in substantiallysimilar amounts other phenolic bactericides such as,2,4,6-trichlorophenol; n-hexyl-o-bromophenol, tetrachlorophenol and thelike, and potentiating agents such as pentasodium amino tri( methylenephosphonate), tetrasodium methylenediphosphate and the like.

We claim:

1. An antiseptic composition comprising a bactericide selected from theclass consisting of phenolic bactericides and, as a potentiating agent,a water-soluble polyphosphonic acid compound having the formula whereinn is an integer from 2 to 3 inclusive, M is a member selected from thegroup consisting of hydrogen, alkali metal ions, ammonium ions and amineions, and Z is a connecting radical equal in valence to n and containingfrom about 1 to about 12 atoms, exclusive of hydrogen, in chemicalcombination, and is selected from the group consisting of alkylideneradicals, halo-substituted alkylidene radicals, hydroxy-substitutedalkylidene radicals, alkylidene amine radicals, dialkylidene amineradicals, and trialkylidene amine radicals, with the proviso that saidpotentiating agent is present in an amount sufficient to improve theactivity of said bactericide.

2. An antiseptic composition comprising a bactericide selected from theclass consisting of phenolic bactericides and, as a potentiating agent,a water-soluble amino tri(lower alkylidene phosphonic acid) compoundhaving the formula XOOH wherein X and Y are members selected from thegroup consisting of hydrogen and lower alkyl, and M is a member selectedfrom the group consisting of hydrogen, alkali metal ions, ammonium ionsand amine ions, with the proviso that said potentiating agent is presentin an amount sufficient to improve the activity of said bactericide.

3. The composition of claim 2, wherein said potentiating agent ispentasodium amino tri(methylene phosphonate).

4. An antiseptic composition comprising a bactericide selected from theclass consisting of phenolic bactericides and, as a potentiating agent,a water-soluble lower alkylidene diphosphonic acid compound having theformula

2. An antiseptic composition comprising a bactericide selected from theclass consisting of phenolic bactericides and, as a potentiating agent,a water-soluble amino tri(lower alkylidene phosphonic acid) compoundhaving the formula wherein X and Y are members selected from the groupconsisting of hydrogen and lower alkyl, and M is a member selected fromthe group consisting of hydrogen, alkali metal ions, ammonium ions andamine ions, with the proviso that said potentiating agent is present inan amount sufficient to improve the activity of said bactericide.
 3. Thecomposition of claim 2, wherein said potentiating agent is pentasodiumamino tri(methylene phosphonate).
 4. An antiseptic compositioncomprising a bactericide selected from the class consisting of phenolicbactericides and, as a potentiating agent, a water-soluble loweralkylidene diphosphonic acid compound having the formula wherein X is amember selected from the group consisting of hydrogen and lower alkyl, Yis a member selected from the group consisting of hydrogen, hydroxyl andlower alkyl, and M is a member selected from the group consisting ofhydrogen, alkali metal ions, ammonium ions and amiNe ions, with theproviso that said potentiating agent is present in an amount sufficientto improve the activity of said bactericide.
 5. The composition of claim4, wherein said potentiating agent is tetrasodium 1-hydroxy, ethylidenediphosphonate.